JPH01209452A - Production of damping-waterless planographic printing plate material - Google Patents

Abstract

PURPOSE:To obtain a damping-waterless planographic printing plate which has excellent coatability and does not flaw the surface of a photosensitive layer by using a base film having a release property and incorporating a surfactant into the photosensitive layer. CONSTITUTION:A photosensitive material is coated on the base film 1 having the release property and is dried to form the photosensitive layer 2, then a silicone rubber layer 3 is formed on the photosensitive layer 2. The surfactant in addition to the photosensitive material are incorporated into the photosensitive layer and more preferably the surfactant is a fluorine surfactant. After the silicone rubber layer 3 side is brought into pressurized contact with the base 4, the silicone rubber layer 3 is cured and the film 1 is stripped, by which the damping-waterless planographic printing plate is obtd. The base film 1 having the good release property is used and the surfactant is incorporated into the photosensitive layer in such a manner; therefore, the coatability of the photosensitive layer is improved without flawing the photosensitive layer surface of the base.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a lithographic printing plate material that does not require dampening water (hereinafter referred to as a dampening water-free plate material or plate material), and specifically relates to a method for producing a lithographic printing plate material that does not require dampening water (hereinafter referred to as a dampening water-free plate material or plate material). The present invention relates to a method for producing a lithographic printing plate material that does not require dampening water and has excellent properties.

[Prior Art] Conventionally, a lithographic printing plate material that does not require dampening water is formed by sequentially laminating a silicone rubber layer and a photosensitive layer on a support, and image areas are formed by exposing and developing the plate material. The technology is known. However, when attempting to coat a silicone rubber layer and a photosensitive layer on a support in order, it is extremely difficult to coat the photosensitive layer uniformly on the silicone rubber layer, and the adhesion between the silicone rubber layer and the photosensitive layer is extremely difficult. There is a problem of insufficient gender. For this purpose, a photosensitive layer is uniformly coated on a base film in advance and then bonded to a silicone rubber layer lined with a support, or a photosensitive layer is coated on a base film and then a silicone rubber layer is coated on top of the base film. Printing materials were manufactured by pasting together the set material and the support (Shokai No. 55-70848, Shokai No. 55-84938, and Shokai No. 5).
0-68304).

[Problems to be Solved by the Invention] In each of the above methods, since it is necessary to peel off the base film, a film with excellent peelability, such as a PP film, is used as the base film.

However, when using a PP film with excellent peelability,
There was a drawback that the photosensitive layer could not be coated because the photosensitive liquid with low viscosity was repelled.

On the other hand, if a film with poor releasability is used in an attempt to improve coating properties, there is a drawback that the surface of the photosensitive layer may be damaged.

[Object of the Invention] Therefore, an object of the present invention is to provide a method for producing a lithographic printing plate material that has excellent coating properties and does not require dampening water and does not damage the surface of the photosensitive layer.

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the inventors have arrived at the present invention.

That is, the method for producing a lithographic printing plate material that does not require dampening water according to the present invention comprises sequentially providing a photosensitive layer and an uncured silicone rubber layer on a releasable base film, and pressing a support onto the silicone rubber layer side. , a method for producing a lithographic printing plate material that does not require dampening water by curing the silicone rubber layer on the support and then peeling off the base film, including containing a surfactant in the photosensitive layer. Features.

[Function] According to the present invention, since a base film with good releasability is used and the photosensitive layer contains a surfactant, it is possible to improve the releasability of the base film and the photosensitive layer while improving the coatability of the photosensitive layer.

[Structure of the Invention] Hereinafter, an example of the method for producing a dampening water-free printing plate according to the present invention will be described with reference to the accompanying drawings.

First, as shown in FIG. 1, a photosensitive material is coated on a releasable base film 1 and dried to form a photosensitive layer 2, and then a silicone rubber layer 3 is formed on the photosensitive layer 2.

Next, as shown in FIG. 2, the silicone rubber layer 3 side is pressure-bonded to the support 4, and then the silicone rubber layer 3 is cured and the base film 1 is peeled off to form a dampening water-less lithographic plate as shown in FIG. Obtain printing plate material. 3' is a silicone rubber layer after curing.

Next, the original film is placed on the photosensitive layer 2 side, exposed, and developed with a developer to form an image area 2' as shown in FIG.
By forming this, a printing plate that does not require dampening water can be obtained.

The above manufacturing method will be explained in more detail.

The base film used in the present invention is a film having peelability, and is preferably a polyolefin film.
Examples include films such as polypropylene (PP) and polyethylene terephthalate (CPET), laminate films of PP and PET, and paper laminated with these polyolefin films.

As the photosensitive substance used in the photosensitive layer, a positive type photosensitive substance is preferably used.

Examples of positive type photosensitive substances include quinonediazide type positive photosensitive substances such as conventionally known 0-naphthoquinonediazide compounds.

Suitable 0-naphthoquinonediazide compounds include:

There are esters of naphthoquinone-(1,2)-diazide-(2)-sulfonic acid chloride with phenol or cresol-formaldehyde resins, as described in U.S. Pat. No. 3,048,120.

Other useful 0-naphthoquinonediazide compounds include, for example, the ester of pyrogallol-acetone resin and 0-naphthoquinonediazide sulfonic acid chloride described in U.S. Pat. No. 3,835,709;
No. 6348, No. 5B-1044 and No. 5$-1045
Polyhydroxyphenyl resin and 0-
Esters of naphthoquinonediazide sulfonic acid chloride, homopolymers of p-hydroxystyrene as described in JP-A-50-113305, or copolymers of this and other copolymerizable heptamers with 0- Products obtained by ester reaction of naphthoquinonediazide sulfonic acid chloride, reaction products of polymer products of styrene monomers and phenol derivatives described in Japanese Patent Publication No. 49-17481 and O-quinonediazide sulfonic acid, and polyhydroxybenzophenone and O- Examples include esters of naphthoquinonediazide sulfonic acid chloride.

A photosensitive composition containing such a quinone diazide type positive photosensitive material may optionally contain a binder. For example, a preferred example is a novolac resin soluble in an aqueous alkali solution. Examples of such novolac resins include phenol-formaldehyde resins,
Typical examples include cresol-formaldehyde resin, p-tert-butylphenol-formaldehyde resin, and phenol-modified xylene resin. The amount of quinonediazide compound in the photosensitive composition is 10-
50 fi amount%, more preferably 20 to 40 fi amount%
It is. Further, the amount of the above-mentioned binder added is 4% in the photosensitive composition.
It is 5 to 80% by weight, preferably 50 to 70% by weight.

Further, the following photosensitive substances can be used as required. For example, a diazo resin typified by a condensate of an aromatic diazonium salt and formaldehyde. Particular preference is given to salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as reaction products of hexafluorophosphates, tetrafluoroborates, perchlorates or periodates with said condensates. Examples include certain diazo resin inorganic salts and diazo resin organic salts which are reaction products of the above condensates and sulfonic acids, as described in US Pat. No. 3,300,309. The diazo resin is preferably used together with a binder. Various polymeric compounds can be used as the binding agent, but monomers having aromatic hydroxyl groups such as those described in JP-A-54-98813, such as N-(4- and/Droxyphenyl) acrylamide,
N-(4-hydroxyphenyl)methacrylamide,
0-, ■-1 or p-hydroxystyrene, o-, m
Copolymer of -1 or p-hydroxyphenyl methacrylate and other monomers, US Pat. No. 4.123.27E
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as a main repeating unit as described in item i, shellac,
Natural resins such as rosin, polyvinyl alcohol, polyamide resins described in U.S. Pat. No. 3,751,257, linear polyurethane resins described in U.S. Pat. No. 3,680,097, phthalated resins of polyvinyl alcohol, Epoxy resins condensed from bisphenol A and epichlorohydrin, celluloses such as cellulose acetate and cellulose acetate phthalate are included.

In addition, 10H=C as a photosensitive group in the main chain or side chain of the polymer.
) 1-C- containing photosensitive polymers such as polyesters, polyamides, and polycarbonates are also included. Photosensitive polyesters obtained by condensation of diethyl acrylate with hydrogenated bisphenol A and triethylene glycol, as described in U.S. Pat. No. 2,958,878,
Examples include photosensitive polyesters prepared from (2-properidene) malonic acid compounds such as cinnamylidene malonic acid and difunctional glycols.

Further examples include aromatic azide compounds in which the azide group is bonded directly or via a carbonyl group or a sulfonyl group to an aromatic ring.For example, polyazidostyrene as described in U.S. Pat. No. 3,098,311 Polyvinyl-p-azidobenzoate, polyvinyl-p-azidobenzal, the reaction product of azidoarylsulfanyl chloride and unsaturated hydrocarbon polymer described in Japanese Patent Publication No. 45-9813, and Japanese Patent Publication No. 43-21087, No. 44-229, No. 44-22954 and No. 45-2
Examples include polymers having sulfonyl azide and carbonyl azide, as described in No. 4915.

Furthermore, a photopolymerizable composition comprising an addition polymerizable unsaturated compound may also be mentioned. The present invention can also be applied to photosensitive compositions used in electrophotographic printing plates. Examples include photosensitive compositions comprising pigments and phenolic resins.

The photosensitive material contains a surfactant in addition to the above-mentioned photosensitive substance.

As the surfactant, nonionic surfactants are preferred, such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid, etc. In addition to esters, polyethylene glycol fatty acid esters, polyoxyethylene fatty acid amines, fatty acid monoglycerides, sorbitan fatty acid esters, pentaerythritol fatty acid esters, propylene glycol fatty acid esters, polyglycerin fatty acid esters, fatty acid alkanolamides, amine oxides, etc., fluorine-based surfactants are used. Among them, fluorine-based surfactants are preferred.

Examples of the fluorine-based surfactant preferably used in the present invention include (meth)acrylate polymers having a fluorinated alkyl group in the side chain, and in this case, the number average molecular weight in terms of standard polystyrene is 30,000 or less. Those with an IQ of 2,000 to 2,000 are preferred, and more preferably 2,000 to 2,000.
It is within the range of

The number average molecular weight of the (meth)acrylate polymer is 30.0
If it exceeds 00, the effect of improving coating properties will not be sufficient.

The acrylate structural unit or methacrylate structural unit of the moiety having a heptafluorinated alkyl group in the side chain in the (meth)acrylate polymer is, for example, the following general formula % formula % (wherein R is a hydrogen atom or a methyl group, , n is O~
20, a represents an integer of 0 to 2, b represents an integer of 0 to l) or the following general formula % formula % (wherein R is a hydrogen atom or a methyl group, and n is 0-
10, Peng is 0-20. a represents an integer from O to 2), specifically 0-CHz(OF?)3CFH20-11;H2(C
F2)3GF3■ 0-CHzCCFz)2oCF3 0-CHzCC
Fz)2ocF2HCH30H3 0-CF20F30-(CF?hCF=-C;H2-C
H--OH2-CH- =CH? -GH- C=O 0-(CF2) +aCFI ■ 0-(CF20F30 -CH2-CH- -C:H2-C:H- -GH2-GH- -CH2-CH- -CH2-CH- -CH2-C :H- ■ -(:H2-CH- -CH2-CH- -C)+2-C)I- ■ -CH? -CH- -(:H2-CH- CH3 -GH2-C- CH3 -cH2-c- CH.

Steam-GH2-C- Less CH3 -CH2-C- Hz -CH2-C- CH3 10H2-c- CH3 -co? -c- CH co-C:H2-C- CH3 -CH2-C- υ CH3 -CH2-G- CH3 -CH2-C- CH3 -C:H2-C- Gate-CH2-C- etc. can. The (meth)acrylate polymer having a fluorinated alkyl group in the side chain preferably further has a fluorinated alkyl group or an alkyl group in the side chain. ) As the 7-acrylate structural unit or methacrylate structural unit of the moiety having an alkylene oxide group in the side chain in the acrylate polymer, for example, the following general formula % formula % (wherein R is a hydrogen atom or a methyl group, n is O~
6, Peng represents an integer from 1 to 10, and can be expressed as
Specifically, the following can be mentioned.

In addition, as the 7-acrylate structural unit or methacrylate structural unit of the part having an alkyl group in the side chain in the (meth)acrylate ffi combination having a fluorinated alkyl group in the side chain, for example, the following general formula % formula % (in the formula , R is a hydrogen atom or a methyl group, and n. is 1
), which represents an integer of ~22, specifically U-L;5H1l Ll
-1y6r113u-1,15H1l
u-shi61113 etc. can be mentioned.

Furthermore, the (meth)acrylate polymer having a fluorinated alkyl group in the side chain may have a 7-aryl group, an arylene group, etc. in the side chain. Examples of the structural unit or methacrylate structural unit include -c++t-co-, -C11, -C11--C11,
-C) l-, -Cll, -CI- Furthermore, (meth) having a fluorinated alkyl in the side chain preferably used in the present invention
The acrylate polymer may contain structural units other than the above, such as -CF2-CF, -, -C11, -'C11-CO0I
It may have I-CH-CI[-, etc.

Also, CrF lsc:02NH4 CaF + rS02N (C2H5) OH2GOO
KC8F,ノSo zNHc lH6N' (OH3
)20 views =CrF +s(:0N)l(CHzhN・
(CH3) 2czHaco Kano CsF + +5O2N
(CzHs)C2Ha(OC3H6) 5OHGrF+
5GOMHCxHs'(CHx)z(1;H2)zCO
O-CaF I 7S02NHCH+ SO3NaCH
2COO- 06F l 3S02NC3HbN・(CHI)2Gs
F l+5OzN-(GHz) 3N'(CH3)
zClbCOO-CIH? C5FIrSO2NHC3H6N・(CH3) 2c
2H50s-02002HsCrF + 5c:0NH
G IH6N゛(OH3) 30 sentences-2H5 C3FusO2NGHzGH20(GH2GH20)+
oH(:aFuSO2N(CHx)CHzC:HzOz
CC)l<HzCsF uS02N(C)13)(-C
)Iz-CH+1o)1C00C2)1s Fluorine-based surfactants such as the following can also be used.

Furthermore, as the fluorine-based surfactant preferably used in the present invention, commercially available products can also be used, such as Surf 0
rS, -38J, rS-382J, rsc-IOI
J, rS C-102J, rS C-103J, rs
C-104J (all manufactured by Asahi Glass Co., Ltd.), Florado rF
C-430J, rFC C-431J, rFC-173
J (all fluorochemicals - Sumitomo 3M Company V),
EFTO/PR rEF352”, rEF 301J, r
EF 303J (both manufactured by Shin-Akita Kasei Co., Ltd.), Schwegofluer r8035J, r8038J (both manufactured by Schwegmann), rB M 100OJ, rBMllo
oJ (all manufactured by BM Himy), etc.

The fluorine content of the fluorine surfactant preferably used in the present invention is preferably 5 to 80g1% by weight.
and more preferably 8 to 65% by weight.

The various fluorosurfactants mentioned above can be used alone or in combination.

The amount of surfactant added is 0 based on the total weight of the photosensitive material.
．． It is preferably 0.0001-10114%, more preferably 0.0001-2%.

A silicone primer can also be added to the photosensitive layer. The silicone brimer has a so-called carbon functional silane as its main component, and has been modified in various ways.

For example, a low molecular weight silane compound such as alkylsilanol, its ester, organoalkoxysilanes, such as alkoxysilane having a glycidoxyprobyl group, or vinyltrichlorosilane, is dissolved in a nonpolar solvent. Commercially available products include PRX-304, 5H-50fi, and 5H-4 manufactured by Toray Silicone.
094, 5H-1800, 5H-2280, Primer ME-11 manufactured by Toshiba Silicone Co., Ltd., and the like.

The amount of silicone primer added is preferably 0.0001 to 10% by weight, more preferably 0.0001 to 2% by weight based on the total weight of the photosensitive material.

To form the photosensitive layer, use a normal coater such as a reverse roll coater, air knife coater, Meyer percoater, etc.
Alternatively, the photosensitive material or the like is applied onto the base film using a spin coating device such as Whaler and dried.

The thickness of the photosensitive layer is preferably 0.05 to 10 g+w, more preferably 0.45 to 5 g+w.

In the present invention, the photosensitive layer coating solution may further contain fillers, dyes, dyes, pigments, surfactants other than the compounds of the present invention for improving coating properties, and other commonly used additives and auxiliaries. Can be done.

The silicone rubber used in the silicone rubber layer of the present invention is preferably one whose main component is a linear organic polysiloxane having a molecular weight of several thousand to several hundred thousand and having the following repeating positions.

(-Si -0+r1 where n is an integer of 2 or more, R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an alkyl group, a vinyl group,
Preferably, it is an aryl group, and 60% or more of R is a methyl group.

The silicone rubber useful in the present invention is obtained by a condensation reaction between such a silicone base polymer and a silicone crosslinking agent as listed below.

(1) R-9i-fl-OR”) (2) R-5i(-OAc) (3) R-9i+0N-CR”z)z Here, R has the same meaning as R explained earlier, and R ' is an alkyl group such as a methyl group or an ethyl group, and AC is an acetyl group.

These silicone rubbers are also available as commercial products, such as Toshiba Silicone Co., Ltd.'s TAYE-3085G.

Other useful silicone rubbers are produced by reacting the base polymers listed above with H-type silicone oils having the following repeating units, or by producing silicone base polymers in which approximately 3% of R is vinyl groups. It can also be obtained by an addition reaction with H-type silicone oil or a reaction between the H-type silicone oils.

(In the formula, R has the same meaning as R above, and n is an integer of 2 or more, and n is O or a !!i number of 1 or more.) In order to obtain silicone rubber by such a crosslinking reaction, In addition to the above ingredients, organic carboxylates of metals such as tin, zinc, cobalt, lead, calcium, and manganese, such as dibutyltin laurate, tin(n) octoate, and cobalt naphthenate, or chloroplatinic acid. Such a catalyst is added.

In addition, in order to improve the strength of silicone rubber and obtain silicone rubber that can withstand the frictional forces generated during printing operations,
Fillers can also be mixed. Silicone rubber pre-mixed with a filler is commercially available as silicone rubber stock or silicone rubber dispersion, and as in the present invention, it can be coated with
If it is preferred to obtain a silicone rubber film, RT
Disversions of V or LTV silicone rubber are preferably used. An example of this is ) -1/
sy+ on 23.5RX-25 manufactured by Ko-y Co., Ltd.
7,5) There are silicone rubber dispersions for paper coating such as 1237.

In the present invention, in addition to the above-mentioned components, a small amount of photosensitizer can be included in the silicone rubber layer.

The thickness of the silicone rubber layer is preferably 0.5 to 100 gts, more preferably 1 to 40 pw.

The means for applying the silicone rubber layer is not particularly limited, and any method may be used as long as an uncured silicone rubber layer is formed, including lamination in addition to general coating.

The support used in the present invention preferably has the flexibility to be set in a normal lithographic printing machine and the ability to withstand the load applied during printing. Typical examples include metal plates such as aluminum, zinc, copper, and steel; Examples include metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., paper, plastic films, glass plates, resin-coated paper, paper covered with metal foil such as aluminum, and the like. Among these, aluminum plates are preferred. When using an aluminum plate, it is preferable to use a known grained or anodized plate.

Examples of methods for graining include mechanical methods and electrolytic etching methods.Mechanical methods include, for example, pole polishing, brush polishing, liquid honing, and eight polishing. The various methods described above can be used alone or in combination depending on the composition of the aluminum material.

Electrolytic etching is carried out in a bath containing one or a mixture of two or more inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid.

After the sand O-standing treatment, if necessary, a desmut treatment is performed using an aqueous alkali or acid solution to neutralize the material, followed by washing with water.

The anodizing treatment uses a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolyte, and the aluminum plate is used as an anode or a solution containing 10% of phosphoric acid, etc.
Examples include a method of electrolyzing with a ~50% aqueous solution at a current density of 1-1 OA/dm''.

It should be noted that these supports may be further coated for the purpose of preventing Halesi reduction and other purposes.

The thickness of the support is preferably 50 to 400 uLta, more preferably 100 to 300 uLta.

The means for curing the silicone rubber layer on the support is not particularly limited, and may be either natural curing (air drying, etc.) or forced curing (heating, etc.).

Examples of the light source used for exposing the photosensitive layer include a mercury lamp generating ultraviolet light, a carbon arc lamp, a xenon lamp, a metal halide lamp, and a fluorescent lamp.

[Effects of the Invention] According to the present invention, it is possible to provide a method for producing a lithographic printing plate material that has excellent coating properties and does not require dampening water and does not damage the surface of the photosensitive layer.

[Example] The present invention will be explained in further detail by giving examples below.

Example 1 The photosensitive composition shown below was coated on the PP side of a coextruded film of polypropylene (PP) and polyethylene terephthalate (PET) using a wire sprayer to a film thickness of 2 g, m.

[Photosensitive composition] φnaphthoquinone-(1,2)-diazide-(2)-5-
Ester compound of sulfonic acid chloride and pyrogallol acetone resin (number average molecular weight Mn" 1850. f
f1ffi average molecule i M, -2200, 1ii ratio 3
0 mol %) 1.7gΦphenol and p-W combination ffIM composite resin of cresol and formaldehyde (the molar ratio of phenol, m-cresol and p-cresol was 30:42:28)
, number average molecular weight M. =1380, weight average molecule ffi
Mn=914Q, manufactured by Sumitomo Duress, product name 5K-10
3) 6.49g* p-te
Ester compound of novolak resin synthesized from rt octylphenol and formaldehyde and naphthoquinone-(1,2)-diazide-(2)-5-sulfonic acid chloride (ball weight average molecular weight M, -1800, condensation rate 50 mol%) 0.16g0 Oil Blue 8603 (dye manufactured by Oriental) 0.06g φEthylene glycol monomethyl ether 33 Chomatasha FC430 (surfactant manufactured by 3M) 0.1g
After drying this at 90° C. x 2 ml, a toluene solution of uncured silicone rubber (Toshiba Silicone Co., Ltd. % YE-3085) was applied so that the cured silicone had an IOBm. After that, the toluene was removed using a hair dryer, and the material was pressed onto an electrolytically grained aluminum plate using a roller. This was left to stand at room temperature for 30 minutes to fully cure the silicone rubber, and then the base film was peeled off. This at 80℃ x 10
It was sufficiently cured with m1n.

A positive printing original was placed on top of this and exposed using an ultraviolet exposure machine. Thereafter, when the image was developed using a heavy-duty PS positive developer 5DR-1 (manufactured by Konica) under standard conditions, a clear image line was obtained. When this was printed by Heidelberg Co., Ltd., %GTO, 2. (100 clean prints were obtained without applying dampening water.

Example 2 After making a plate in the same manner as Example 1, 180°C x 2
When heat treated with 0mln and printed test in the same way, 1
0.000 clean prints were obtained without applying dampening water.

Comparative Example 1 The photosensitive solution used in Example 1, minus FC430, was applied onto PP in the same manner, but repellency occurred and the application was not successful.

Comparative Example 2 The photosensitive solution used in Example 1 was extracted and applied onto PET in the same manner, and silicone was similarly applied and transfer was attempted, but part of the photosensitive layer could not be completely transferred. I made a plate of a relatively clean part and ran it through a printing machine, and it turned out to be 100.
The photosensitive layer disappeared at the end of the sheet.

[Brief explanation of the drawing]

FIGS. 1 to 4 are enlarged cross-sectional views of essential parts showing an example of the method for manufacturing the plate material of the present invention. 12 Base film 2: Photosensitive layer 2': Image area 3: Silicone rubber layer 3': Cured silicone rubber layer 4: Support Patent applicant Nobuaki Sakaguchi □３ Figure 2 Figure 3 Figure 4

Claims (1)

[Claims] A photosensitive layer and an uncured silicone rubber layer are sequentially provided on a base film having peelability, a support is pressure-bonded to the silicone rubber layer side, the silicone rubber layer is cured on the support, and then the base film is removed. A method for producing a lithographic printing plate material that does not require dampening water by peeling, the method comprising containing a surfactant in the photosensitive layer.